Diphenylamine sulfonamide



Patented June 28, 1949 UNITED STATES PAT OFFICE,

DIPHENYLAMINE- SULFONAMIDE. DYE STUFFS N Drawing. Application March-5, 1946; S'erial'No. 652L234 novel: diphenyl'amine dyestuffs suitable for the dyeing of cellulose acetate or other organic'deri-vative of;cellulose materials.

An object of this" invention is the preparation ofiimproved diphenylamine dyestuffs dyeing in golden-yellow to golden-brown shades and having an excellent degree of aifinity for cellulose acetate or other organic derivative of cellulose textile materials.

Another object of this invention is the dyein of cellulose acetate or other organic derivative of cellulose materials with said novel dyestufis whereby dyed materials which do-not bleed when either wet or dry and which exhibit excellent resistance tolight', washing-and acid-fading may be obtained.

Other objects of this invention will appear from the following detailed description.

A wide variety of dyestuffs for cellulose acetate 01 other organic derivative of cellulose textile materials is available in a substantially complete-range of shades. However, certain shades which are available are not sufiiciently fast to one or another of the various agencies which tend to cause undesirable changes in the shade of the dyed textile material. For example, such changes in shade may take place as a result of washing or on prolonged exposure to ultra-violet. light. Certain other dyes are prone to wetordry bleeding and, under the influence of heat and pressure, or during ironing, tend to transfer or markoff from dyed portions of the fabric to undyed portions. All of. these propertiesare obviously undesirable and improved dyestufis dyeing in attractiveshades. and.fr.ee.of.. the above and other disadvantageous: characteristics are constantly sought.

We have now found'that diphenylamine dyestuffs of the general formula:

wherein R: and B may be hydrogen oran: alkyl group such as, for example; methyl, ethyl, propyl, isopropyl, butyl amyl, hexy-l,-.octyl, decyl or dodecyl, a hydroxyalkyl group containing one or more hydroxy groupssuch as, for example, hydroxyethyl, hydroxymethylg hydroxypropyl or diliydroxypropyl; or an acyl group such as, for example, an acetyl, propionyl, or butyryl group; form a class of dyestuffs which are particularly 2.- suitable for dyeing celluloseacetate or other organic derivative of cellulosematerials in fast, golden-yellow to golden-brown: shades of superior resis-tanceto wet or: dry bleeding, toIight, washing and'to various. other detrimentaliagencies.

The novel dyestuffs. of our invention may be prepared by condensing 4chloro-3-nitro-benzenesulfonamide witha the? desired para-aminosubstituted aniline in the presence of an acid binding agent, such as sodium carbonate. As examples of suitable: para-substituted anilineswhich may be employed in forming the novel dyestuffs of our invention there may be mentioned p-amino-acetanilide; p-amino-propionanilide; p-amino-N-methyl-acetanilide, p-amino- N- methyl propionanilide, p-amino-N-hydroxyethyl acetanilida.p..--phenylene'- diamine, p-dimethylamino-aniline, prdiethylamino-aniline, p'-- (methyl-fi-hydroxyethyl) -amino-aniline, p'- (ethyl-p-hydroxyethyl) -amino-aniline, p-di- (18 hydroxyethyl) -amino-ani1ine; p-di+(/i-hydrox-ypro.- pyl) -amino-aniline;. pdir-(fi-u-dihydroxypropyl) amino-aniline, p mono- (,B-hydroxyethyl) -amino=-aniline;, p-- mono- ([i-hydroxy-propyl) -amino aniline, andpmono 3-o-dihydroxypropyl) amino-aniline.

Preferably, the condensation-reaction is carried outiemployinga suitablemediunr such as, for example,- Water, an organic liquid, such as the mono-ethylether of ethylene-glycol, or inan excess of theamine, whichexcess' acts as a solvent during the condensation. Other solvents which may be employed are, for example, ethyl alcohol, amyl alcohol; methylZCel1osolve orxethyleneglycolmonoacetate;

When the condensation reactionis" carried out in a medium com-prising water; an organic liquid such asthe mono-ethyl-ieth'er' of; ethylene glycol or-in another inert liquid;medium which takesnopart' in the. reaction; the reaction is effected-by employing from 1 to-3rm0ls of the=para-aminosubstituted aniline for' each mol of 4-chloro-3' n-itro-benzene sulfonamide' employed; Usually, reflux is employed: where-.the-reaction: is carried out in=an inert'liquidmedium, a temperature of 'to 140 C. being maintained until thexcondensation-reactioniis: completed, say, in 4 to 12 hours; Where an excess of the amine-isemployed as the reactionmedium, fromB- to 5x-mols of the amine may be employed for'each mol. of? 4-chlor0-3- intro-benzene sulfonamide, the reaction; being carried out at a temperature sufiiciently high'to maintain the reactants in a molten condition, 1. e. from to C. Under these conditions the reaction may be completed in from about 2 to 6 hours.

The dyestuffs formed may be recovered from the reaction mass, where a melt condensation reaction is employed, by drowning the molten reaction mass in water and filtering off the insoluble dyestuff which precipitates. Where a liquid medium such as water is employed to effect the condensation reaction, the insoluble dyestufi formed usually crystallizes out as the reaction proceeds and may be recovered by filtration. Recovery of the dyestuffs from a reaction medium comprising an organic liquid may be eifected by steam-distilling the excess amine and organic liquid from the reaction mass and then filtering the solid dyestufi from the aqueous medium remaining. Excellent yields of said novel dyestuffs may be obtained.

While we preferably employ sodium carbonate as the acid-binding agent during the condensation reaction, other acid binding agents such as sodium acetate, magnesium oxide, calcium carbonate or calcium hydroxide may be employed.

In order further to illustrate our invention but without being limited thereto the following examples are given:

Earample I 237 parts by weight of dry 4-chloro-3-nitrobenzene sulfonamide, 450 parts by weight of pamino-acetanilide and 55 parts by weight of sodium carbonate are melted together with stirring. The reaction mixture obtained is stirred at 130 C. for 6 hours during which time it turns brown in color. After heating for 6 hours, the molten mass is poured with stirring into 500 parts by weight of hydrochloric acid (specific gravity 1.18) dissolved in 5000 parts by weight of water, the resulting dilute hydrochloric acid being maintained at 80 C. The mass is stirred for 30 minutes and the precipitated dyestuif is then filtered employing suction. The press cake is resludged with 1000 parts by weight of water heated to 80 0., and the dyestuff is again filtered under suction, the suction being maintained until the press cake is nearly dry. 335 parts by weight of 4- acetamino-Z-nitro diphenylamine-i-sulfonamide are obtained which is equivalent to a yield of 95%. The dyestuff dyes cellulose acetate materials in golden-yellow shades. The dyed material exhibits an excellent degree of fastness to light, dry bleeding, washing and to acid fading.

Example II 237 parts by weight of dry 4-chlor0-3-nitrobenzene sulfonamide, 2'70 parts by weight of para- (ethyl-fi-hydroxyethyl)-amino-aniline, 55 parts by weight of sodium carbonate and 2500 parts by weight of water are heated to reflux, i. e. 100 C. while stirring, the reaction mixture being maintained under reflux for 3 hours. The condensation reaction takes place quite rapidly and the dyestuif separates from solution as an 011. At the completion of the reaction, the oil may be dissolved in aqueous hydrochloric acid and salted from the solution as the hydrochloride. 340 parts by weight of 4:-(ethyl-B-hydroxyethyl)- amino 2 nitro diphenyl-amine-4-sulfonamide are obtained comprising a yield of 90%. This dyestuff dyes cellulose acetate materials in goldenbrown shades and the dyed materials exhibit excellent resistance to dry bleeding, washing and light.

Example III 237 parts by weight of dry 4-chloro-3-nitrobenzene sulfonamide, 2'72 parts by weight of paradimethylamino-aniline, parts by weight of sodium carbonate and 2500 parts by weight of the monoethyl ether of ethylene glycol are heated under reflux, i. e. at 135 0., for 10 hours. The reaction mixture turns a red-brown color. The excess para-dimethylamino-aniline and monoethyl ether of ethylene glycol are removed by steam distillation. The solid dyestuff is filtered off, washed and dried. 320 parts by weight of 4-dimethylamino 2 nitro diphenylamine 4 sulfonamide are obtained, which is equivalent to a yield of This dyestuff dyes cellulose acetate materials in warm golden-tan shades, exhibiting excellent resistance to washing, dry bleeding and light.

It is to be understood that the foregoing detailed description is given merely by way of illustration and that many variations may be made therein without departing from the spirit of our invention.

Havin described our invention what We desire to secure by Letters Patent is:

1. Diphenylamine dyestuffs 0f the following general formula:

I IO:

wherein R and R are members of the group consisting of hydrogen, alkyl, hydroxyalkyl and lower alkyl carbonyl acyl radicals.

2. The diphenylamine dyestuif of the following formula:

3. The diphenylamine dyestufi of the following formula:

4. The diphenylamine dyestuff of the following formula:

GEORGE W. SEYMOUR. VICTOR S. SALVIN. WILFORD DONALD JONES.

REFERENCES CITED The following referenlces are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,709,292 Wagner Apr. 16, 1929 2,080,704 Fischer et al May 18, 1937 OTHER REFERENCES Fischer, Berichte deutsche Chem. GeselL, vol. 24, (1891), p. 3794.

Ullman, Liebigs Annalen, vol. 366 (1909), p. 107.

Certificate of Correction Patent N 0. 2,474,333

GEORGE W.

It is hereby certified numbered patent Oolu and

a a etters Patent sh 11d be same may conform to the record of igned and sealed th THOMAS F.

MURPHY, Assistant Uommz'm'oner of Patents. 

